Acceleration of the reaction between butyl rubber and dimethylol phenols by means of chlorinated paraffin wax and product obtained thereby



United States Patent 2,727,874 ACCELERATION OF THE REACTION BETWEEN BUTYL RUBBER AND DHWETHYLOL PHENOLS BY MEANS OF CHLORINATED PARAFFHV WAX AND PRODUCT OBTAINED THEREBY Lester C. Peterson and Harvey J. Batts, Indianapolis, Ind, assignors to United States Rubber Company, New York, N. Y., a corporation of New Jersey No Drawing. Application December 31, 1952, Serial No. 329,127

17 Claims. (Cl. 260-485) This invention relates to a process for chemically modifying Butyl rubber, and more particularly it relates to a process for accelerating the reaction between Butyl rubher and dimethylol phenols, as Well as to improved products obtained thereby.

A copending application of Tawney and Little, Serial No. 266,146, filed January 12, 1952, now U. S. Patent 2,701,895, discloses and claims the vulcanization of Butyl rubber with dimethylol phenols. It has been desired to render the vulcanization of Butyl rubber with dimethylol phenols more convenient and more economical, by reducing the time and temperature necessary to attain a practical cure by this method. Accordingly, the principal object of the present invention is to provide a method of accelerating the aforesaid vulcanization process.

We have now discovered that the cure of Butyl rubber with dimethylol phenols is greatly accelerated in the presence of a small amount of chlorinated paraffin wax, and excellent cures can be obtained in a considerably shorter time, or at a lower temperature, than would otherwise be possible.

Butyl rubber, as is well known, is the type of synthetic rubber made by copolymerizing an isoolefin, usually isobutylene, with a minor proportion of a multi-olefinic unsaturate having from 4 to 14 carbon atoms per molecule. The isoolefins used generally have from 4 to 7 carbon atoms, and such isomonoolefins as isobutylcne or ethyl methyl ethylene are preferred. The multi-olefinic unsaturate usually is an aliphatic conjugated diolefin having from 4 to 6 carbon atoms, and is preferably isoprene or butadiene. Other suitable diolefins that may be mentioned are such compounds as piperylene; 2,3-dimethyl butadiene-l,3; 1,2-dimethyl butadiene-l,3; 1,3-dimethyl butadiene-l,3; l-ethyl butadiene-L3; and 1,4-dimethyl butadienc-l,3. The Butyl rubber contains only relatively small amounts of copolymerized diene, typically from about 0.5 to and seldom more than 10%, on the total weight of the elastomer. For the sake of convenience and brevity, the various possible synthetic rubbers within this class will be designated generally by the term Butyl rubber.

The dimethylol phenols employed as curing agents in the process of the invention are known materials. The dimethylol phenol employed may be essentially a monomeric material, or it may be a polymeric material formed by self-condensation of the dimethylol phenol to yield a heat-reactive, oil-soluble, resinous product. Such resinous polymeric dimethylol phenols are the preferred materials for use in manufacturing the puncture-sealant from Butyl rubber in accordance with the method of the invention. Mixtures of the resinous polymeric dimethylol phenols with more or less of low molecular weight or monomeric dimethylol phenols are also useful. For convenience, the term dimethylol phenol will be used to refer to any of the monomeric or polymeric compounds, or to mixtures thereof, unless otherwise stated.

As will be understood by those skilled in the art, the dimethylol phenols are typically made by reacting a parasubstituted phenol having the two ortho positions unocorganic solvents and drying oils) and fusible state.

cupied, with a considerable molar excess of formaldehyde, the molar ratio of formaldehyde to phenol typically being 2:1, in the presence of a strong alkaline catalyst, especially an alkali metal hydroxide, which is subsequently neutralized. Typically the mixture of the phenol, formaldehyde and alkaline catalyst is heated at a suitable temperature, e. g., 25-100 C., the first stage of the reaction involving formation of the phenol methylol, i. e., the para-substituted-2,6-dimethylol phenol. This material, which is a phenol dialcohol, can be isolated by acidification of the mixture and separation of the oily layer which can then be advanced to higher molecular weight form by heating at say -175 C. This higher molecular weight form is oil-soluble and heat-reactive, and has the advantages that it is more reactive with the Butyl rubber than the lower molecular weight form. Separation of the phenol dialcohol can be omitted, in which case the reaction is carried past the monomer stage to the resinous stage, whereupon the mixture is neutralized and water is removed to give the resinous material. In any case, care should be taken to stop while the resin is in the soluble (in conventional This is the resol type of resin.

The phenol from which the dimethylol phenol is made generally has a hydrocarbon group in the position para to the phenolic hydroxyl, examples being alkyl groups, especially alkyl groups having from 3 to 20 carbon atoms, tertiary-butyl and tertiary-octyl (alpha, alpha, gamma, gamma-tetramethyl butyl) being especially preferred, cycloalkyl groups, aryl groups such as phenyl, and aralkyl groups such as benzyl and cumyl. We believe that the tertiary-butyl and the aforementioned branched octyl are outstanding. Examples of suitable dimethylol phenols that may be used in the invention either in the polymeric or monomeric form are as follows:

2,6-dimethylol-4-methyl phenol 2,6-dirnethylol-4-tertiary-butyl phenol 2,6-dirnethylol-4-octyl phenol 2,6-dimethylol-4-dodecyl phenol 2,6-dimethylol-4-phenyl phenol 2,6-dimethylol-4-benzyl phenol 2,6-dimethylol-4-(alpha, alpha-dimethyl benzyl) phenol 2,6-dirnethylol4-cyclohexyl phenol The resinous forms of these materials, prepared as described, are preferred, especially when derived from the lower alkyls (8 carbon atoms or less). The dimethylol phenol is generally employed in amount within the range of from about 2 to 15 parts by weight to parts of the Butyl rubber.v While smaller amounts of the dimethylol phenol may be employed, e. g. 1 part, it is usually found that less than this amount is insufiicient to produce a practical cure within a reasonable time. However, if actual substantial vulcanization is not desired, and a limited or partial reaction is all that is involved, very small amounts may be used, as will be more fully explained below. Also, larger amounts may be used, c. g., 20 parts, but amounts greater than this are Without further advantage.

In accordance with a preferred embodiment of the invention, the Butyl rubber is compounded for vulcanization with a dimethylol phenol, using a chlorinated paratfin as an accelerator. The chlorinated paraffins are known materials, made by chlorination of paratfin waxes. They may be liquid, semi-fluid, or solid, depending upon the type of paraffin and the degree of chlorination. The amount of chlorine in chlorinated parafiins varies Widely (e. g. 10-80%), and for purposes of the invention the chlorine content is not critical, but it may be stated that the chlorine content of the typical commercial grades of chlorinated paraflins is generally of the order of from 30% to 70%, with the solid productsusually containing Patented Dec. 20, 1955 about 70% chlorine, and the liquid and semi-fluid products usually containing about 40-50% chlorine. The products marketed under such trade designations as Clorafin, Chloroparafiin, Chlorowax, and are repthe mixture to enhance the accelerating effect of the chlorinated paraflin, sustained high temperatures should be avoided during the mixing operation, to prevent undesired premature reaction.

1 Samples dissolved. l Swollen to rupture andunflt (or tent.

resentative of the commercial chlorinated parafiins. 5 The vulcanizable mixture resulting from the foregoing The amount of chlorinated parafiin employed in the ingredients may be fabricated into the desired form by. invention may vary considerably, but usually only a very the usual methods, such as calendering, extrusion, or small amount is used, since the chlorinated paraflins are molding, and subsequently vulcanized by heating, prefquite potent in their accelerating action. Thus, definite erably while confined under pressure. accelerating efiect may be noted with as little as a few For the purpose of making such articles as curing bags tenths of a part of the chlorinated paraifin in 100 parts or inner tubes, there is generally included in the mixture of Butyl rubber, although we generally use somewhat a quantity of a suitable reinforcing material, preferably more than this, say 3 to 10 parts per 100'parts of the carbon black. Although from at least about 20 to 100 Butyl. Although even larger amounts of the accelerator parts by Weight of carbon black may be employed per can be used, say or parts, it is not generally neces- 15 100 parts of the butyl rubber, it is generally preferred to sary or desirable to use appreciably more than about 10 use from about 40 to 80 parts of black, and most prefparts. erably about 50 or 60 parts. Other conventional fillers, We have further found that the accelerating effect of such as clay, zinc oxide, iron oxide, etc., may also be used. the chlorinated parafiins can be enhanced greatly by the Other conventional compounding ingredients, such as presence of small amounts of heavy metal compounds, 20 processing aids, may be included in the mixture if desired. especially heavy metal oxides, or heavy metal salts. Thus, The curing process of the invention is conveniently carthe oxides of iron, zinc, tin, lead, aluminum, manganese, ried out at a temperature of 200 F. or more, and prefor other heavy metals, or salts of-such metals with organic erably at temperatures in excess of 300 F., for periods or inorganic acids, such as carbonic acid, chromic acid, of time ranging from about 5 minutes to 3 hours, the acetic acid, stearic acid, lauric acid, etc., can be used as longer periods of time Within the stated time range being activators of the chlorinated paraffin acceleration. For employed with the lower temperatures. The most preexample, the addition of 1l0 parts of zinc oxide to the ferred vulcanizing temperatures are within the range of vulcanizable mix will further decrease the time or temabout 320 to 370 F., although somewhat higher tem-- perature necessary for adequate cure-., peratures may be employed, e. g., 390 or 400 F., pro- In "carrying out the invention, the butyl rubber, divided that such highly elevated temperatures are not mainmethylol phenol, and chlorinated parafiin, and any tained for a sufficiently long time to cause thermal injury additional desired ingredients, may be mixed together in to the article. any desired order according to the procedures ordinarily The following examples will serve to illustrate the inused in mixing rubber compounds, with the aid of the vention in more detail. In the examples, the amounts of usual rubber mixing equipment, such as an internal mixer the various ingredients are all expressed in terms of parts or roll mills. If a heavy metal compound is included in by weight.

Table I I1 r-z r-s' 1-4 1-5 I-s r-7 I-8 I-9 Ingredients:

GR-T 1s 100 100 100 100 100 100 100 100 100 Clorafin 42 1 5 10 1 5 10 5 S0 137 Resin- 12 12 12 12 12 12 12 12 12 Philhlack 0 (Carbon blaek).--. 60 60 e0 60 60 Zinc Oxid 3 Cure at Properties:

Tensile Strength, p. 5.1 3 ggg 45' 430 270 245 220 5' 1,100+ 1,100+ 10: 1,100+ 1,100 Elongation at Break, percent... 58, gg .45 830 770 so 680 650 5 17 24 10' 12 18 300% Modulus, p. 5.1 8: 2g 45'. 4a 52 60' 49 so 5' 17 2A 10: 12 18 500% Modulus lg, 45' 62 104 60 105 5' 27 27 10: 2s 28 Hardness, Shore A $5, 3 45' 28 2s 6(5): 1 29 )28 Percent Volume Increase in Cyclohexanein hrs. at 75 333 F 30' 693 ss3 45 614 564 60 584 564 a; 344 348 Williams Plasticity Number at 212 F 30' 395 915 45' 929 944 60 940 947 EXAMPLE I cure. a The Williams plasticities, however, are quite satis- Nine separate stocks were made up by mixing on a mill facml'y for thls taskthe materials shown in Table I in the stated amounts. Portions of the stocks were cured for varying times as indicated, and the properties of the resulting vulcanizates 5 EXAMPLE n were measured, with the results noted in the table. The I GR-I 18 is a commercial grade of synthetic rubber made To determine the antioxidant characteristics f the V111- by copolymerizing isobutylene and isoprene, and containeaniletes 0f the invention, Stocks and 9 0f ing about 2 /2% of combined isoprene. The Clorafin 42 Example I were subjected t0 an aging test The Stocks is a commercial chlorinated parafiin having the form ofa were first Dre-Cured in a Slab m Stoc I5 Was viscous liquid and containing about 42% chlorine. The Cured minutes at 's While Stocks nd Amberol ST-137 is a commercial phenolic resin of the were Cured y 15 minutes, in Order to ndimethylol phenol class, and it is believed to be made from strate that the antioxidant effeet was not due 10 a highb t 1 l f p-octyl h l, 2 moles f fo aldehyde er state of cure in the accelerated stock. The pre-cured and 1 mole of sodium hydroxide, the alkali being care- 15 Stocks were then heated to a tempefatulfe 0f fully neutralized after the condensation is complete. in an air pressure cure mold, having metal on one sur- In stocks I-1 to 14 of Table I no carbon bla k i face and air on the other, for a period of 16 hours unpresent. Stock H is a control containing no Clorafin der a pressure of pounds per square inch. This test 42, and stocks I-2 to I-4 contain increasing quantities was Severe enough t0 completely degrade a Standard f cl afi 42, St cks L5 to L9 co tain rb bl k, stock. The results ofthe test are indicated in Table II.

Table II ANTIOXIDANT TEST Original Aged Percent Original Stock 1-5 I-7 I-9 I-5 I-7 1-9 1-5 1-7 In Physical Properties: 1

Tensile 2, 030 1, 660 1,820 1,200 6.15 9. 05 66 Elongation 440 520 530 440 500 270 100 96 51 300%Modulus 1,450 790 855 105 115 Stock I-S is a control and stocks I-6 to I-8 contain in- The data of Table II indicate that stock I-9, containcreasing amounts of Clorafin 42, While stock I-9 furr ing Clorafin 42 plus zinc oxide, is remarkably resistant ther includes zinc oxide. Perhaps the most significant to oxidation, compared to stock I-7 containing Cloraresults shown in Table I are the figures on the amount fin 42 but 110 Zinc OXide, s l a ompared to the conof swelling of the cured stocks in cyclohexane. Such U01 Stock I-S containing no Clorafin 42. equilibrium swell data is recognized as one of the most EXAMPLE In accurate methods of defining the amount of cross-linkage in Butyl. The results clearly indicate the accelerat- This example further illustrates the activation of the ing effect of Clorafin 42, and the greater accelerating chlorinated parafiin acceleration by means of combined effect of Clorafin 42 plus zinc oxide. By comparison, heavy metals. The stocks shown in the table were hot typical sulfur cures of Butyl may require 6-22 minutes milled for 5 minutes at 225 F. to disperse the resin. In cure at 350 F. to attain minimum swell values of 430- 45 the case of stock III-7, the zinc acetate was added as an 5()()% v aqueous solution prior to addition of the resin, and the In the resin cured gum Butyl compounds the tensile stock was milled for 15 minutes at 235 F.-to eliminate and modulus characteristics are low, and such tests are water, after which the Clorafin 42 and the resin were therefore inadequate for defining difierences in states of added to complete the mix.

Table III III-1 III-2 III-3 III-4 III-5 III-6 III-7 III-8 Ingredients:

Zinc Chromafn Zinc Car Zinc Stearate Zinc Laurate Zinc Acetate Black Iron Oririe Cured at 0 F. .2 as Properties: v

Tensile 45' 21045 60 2, 060

910 050 10: 780 390 Elongation g8, 338 45' 610 310 60' 550 330 180 510 12 as 923 1212 1'5 10- 1,880 1,420 1,870 300% M'Jdums a0 ass 1,830 1,090 1,800 1,990 1,900 1, 310 2,240 e 45' 090 1,835- 1,215. 2,000 2,000 1,910 1,220 1,

' Table III.-Continued III-1 111-2 III-3 111-4 111-5 III-s III-7 III-8 5' 440 1, 650 1, 135 1, 495 1, 730 1, e30 905 1, 970 10; 320 2,420 1, 580 2, 230 500% Modulus ,3, {2 kgg 50' 1, 90s 5' 46 5a 54 53 55 52 50 53 I 2 2 a a 22 25 a s a 1 1 Hardness so 55 e4 s5 s7 s9 s9 7a 67 45 59 66 s7 s9 71 70 14 as so 59 as 68 e9 71 71 74 69 Hot Flow 15' 5s 2 s is 2 s 1 2 s 7 5 0 30' 36 4:9 '14 '10 '0 2:5 717 2.4 24 Hrs 15 s 9. s 22 12. 2 5. 1 2. s 7. 5 2. 4 30' 55 7.3 V 14 12.5 2.4 V 5 10.3 2.4 48 Hrs 12. 2 2a 14 e 5. 1 4. 9 1o 2. 4 50' as 15.3 12.5 2.4 5 10.3 2.4

indlca EXAMPLE IV the other stock. Clorafin 428 is similar to Clorafin 42,

but is stabilized for better clarity and color.

Table IV IV-1 IV-2 Ingredients:

G 11-1 18 100 100 EPO Carbon Black 60 60 Stearie Acid 1 1 10 10 5: l, 780 1, e50 it an Tensfle a0 2, 100 2, 110

2, 050 2, 040 40 60' 2, 040 l, 990 5' 860 670 10; 450 s Elongation .4 g3, g2? 45' 530 340 5' 295 490 5. :0: l, 2%5 740 1 ,3. 2 8 13 8 45 1, 850 l, 800 60' 1, 930 l, 750 500% Modulus 5 840 1, 300

5' 54 53 50 10: 63 Hardness (Shore A) g3. 2g 2g 45' 71 5 60 73 70 Mooney Plasticity -4 60 69 67 Hot Flowz 6 Hrs 3,3, '5 3 {.5

taken of'the superior ability of the dimethylol phenol vulcanizates to resist heat, without added cost. The invention therefore provides economical vulcanizates having increased service life, especially in applications where the vulcanizate is exposed to the influence of steam or oxygen. The dimethylol phenol cured products also have It is also possible to reduce the.

Pgrcent elongation under an original stress 0150 p. s. i. applied at a temperature of 340 F. for the times to the advantage that bloom can be avoided, because of the absence of sulfur curatives.

The improved vulcanizates of the invention can be used to great advantage in making a variety of useful articles, such as curing bags, curing blankets, or curing domes of the various known kinds, either for new tires or for re treading tires, as well as in making hose, belts, inner tubes, especially heavy service inner tubes, and pneumatic tires, especially tire treads and side walls, as well as other objects.

The process of the invention has been described with particular reference to the use of chlorinated parafiin wax to accelerate the dimethylolphenol cure of Butylrubber, wherein it was desired to substantially completely cure the Butyl rubber. However, it will be understood that the accelerating cflfect of the chlorinated parafiin on the reaction between the dimethylol phenol and Butyl rubber can be taken advantage of also in processes where only a limited or partial chemical modification of the Butyl rubber by the dimethylol phenol takes place. In such cases, the limited or partial reaction can be carried out in a shorter time, or at a lower temperature, by using the chlorinated paraflin as accelerator in accordance with the invention. Thus, for example, the partial reaction between Butyl rubber and limited amounts of dimethylol phenol, for example, 0.2 to 2.5 parts per parts of Butyl rubber, carried out at temperatures of 200400 F. for from 5 to 45 minutes, can be effectively accelerated by the presence of a small amount of chlorinated parafiin as described. Butyl rubber partially reacted with dimethylol phenol and the process of making the same are disclosed in more detail and claimed in copending application Serial No. 290,344, filed May 27, 1952 now U. S. Patent 2,702,287.

Having thus described our invention, what we claim and desire to protect by Letters Patent is:

1. ,In the method of chemically modifying a rubbery copolymer of an isoolefin having from 4 to 7 carbon atoms with from 0.5 to 10% 0f analiphatic conjugated diolefin having from 4 to 6 carbon atoms by heating 100 parts of said rubber at a temperature of from 200 to 400 F. for from 5 minutes to 3 hours in admixture with from 0.2 to 20 parts of a 2,6-dimethylol4-hydrocarbon phenol wherein said hydrocarbon is a radical selected from the group consisting of alkyl having from 1 to 20 carbon atoms, cycloalkyl, aryl and aralkyl radicals, the improvement which comprises the step of carrying out the said modification in the presence of from a few tenths of a part to 20 parts of chlorinated paraffin wax to accelerate the said modification reaction.

2. A method as in claim 1 in which the said 2,6-dimethy'lol-4-hydrocarbon phenol is an oil-soluble, heatreactive resol resin.

3. A method as in claim 2 in which the said modification is carried out in the presence of at least one part of a heavy metal compound selected from the group consisting of heavy metal oxides and heavy metal salts to activate the said accelerator.

4. A method of vulcanizing a rubbery copolymer of an isoolefin having from 4 to 7 carbon atoms with from 0.5 to of an aliphatic conjugated diolefin having from 4 to 6 carbon atoms comprising the step of heating 100 parts of the said rubber at a temperature of from 200 to 400 F. for from 5 minutes to 3 hours in admixture with from 1 to 20 parts of a 2,6-dimethyloltr-hydrocarbon phenol wherein said hydrocarbon is a radical selected from the group consisting of alkyl having from 1 to 20 carbon atoms, cycloalkyl, aryl and aralkyl radicals, and from a few tenths of a part to 20 parts of chlorinated paraflin wax to accelerate the said vulcanization.

5. A method of vulcanizing a rubbery copolymer of isobutylene with from 0.5 to 5% of isoprene comprising the step of heating 100 parts of the said rubber at a temperature of from 200 to 400 F. for from 5 minutes to 3 hours in admixture with from 2 to parts of an oil-soluble, heat-reactive resol resin which is a 2,6-dimethylol-4-hydrocarbon phenol wherein said hydrocarbon is a radical selected from the group consisting of alkyl having from 1 to carbon atoms, cycloalkyl, aryl and aralkyl radicals, and from 3 to 10 parts of chlorinated parafiin wax to accelerate the said vulcanization.

6. A method as in claim 5 in which the said hydrocarbon radical is a lower alkyl group.

7. A method as in claim 6 in which the said lower alkyl group is tertiary butyl.

8. A method as in claim 6 in which the said lower alkyl group is octyl.

9. A method as in claim 5 in which the said vulcanization is carried out in the presence of a heavy metal compound selected from the group consisting of heavy metal oxides and heavy metal salts, in amount sutlicient to activate the said accelerator.

10. A method as in claim 9 in which the said lower alkyl group is tertiary butyl.

11. A method as in claim 9 in which the said lower alkyl group is octyl.

12. A method as in claim 9 in which the said lower alkyl group is octyl and the said heavy metal compound is zinc oxide.

13. A method as in claim 9 in which the said lower alkyl group is octyl and the said heavy metal compound is a zinc salt of a fatty acid.

14. A method as in claim 9 in which the said lower alkyl group is octyl and the said heavy metal compound is iron oxide.

15. A vulcanizate characterized by improved resistance to aging comprising parts of a rubbery copolymer of an isoolefin having from 4 to 7 carbon atoms with from 0.5 to 10% of an aliphatic conjugated diolefin having from 4 to 6 carbon atoms vulcanized with from 1 to 20 parts of an oil-soluble, heat-reactive resol resin which is a 2,6-dimethylol-4-hydrocarbon phenol wherein the hydrocarbon radical is selected from the group con sisting of alkyl having from 1 to 20 carbon atoms, cycloalkyl, aryl and aralkyl, in amount of from 1 to 20 parts, and accelerated with from 3 to 20 parts of chlorinated paratfin wax.

16. A vulcanizate as in claim 15 in which the hydrocarbon radical is a lower alkyl group.

17. A vulcanizate as in claim 16 in which the alkyl group is octyl.

References Cited in the file of this patent UNITED STATES PATENTS Smith Mar. 20, 1951 OTHER REFERENCES 

1. IN THE METHOD OF CHEMICALLY MODIFYING A RUBBERY COPOLYMER OF AN ISOOLEFIN HAVING FROM 4 TO 7 CARBON ATOMS WITH FROM 0.5 TO 10% OF AN ILIPHATIC CONJUGATED DIOLEFIN HAVING FROM 4 TO 6 CARBON ATOMS BY HEATING 100 PARTS OF SAID RUBBER AT A TEMPERATURE OF FROM 200* TO 400* F. FOR FROM 5 MINUTES TO 3 HOURS IN ADMIXTURE WITH FROM 0.2 TO 20 PARTS OF A 2,6-DIMETHYLOL-4-HYDROCARBON PHENOL WHEREIN SAID HYDROCARBON IS A RADICAL SELECTED FROM THE GROUP CONSISTING OF ALKYL HAVING FROM 1 TO 20 CARBON ATOMS, CYCLOALKYL, ARYL AND ARALKYL RADICALS, THE IMPROVEMENT WHICH COMPRISES THE STEP OF CARRYING OUT THE SAID MODIFICATION IN THE PRESENCE OF FROM A FEW TENTHS OF A PART 20 PARTS OF CHLORINATED PARAFFIN WAX TO ACCELERATE THE SAID MODIFICATION REACTION. 